The solubility of four copper ligand systems in supercritical (SC) CO 2 was studied. Three of the ligand systems studied were commercial ligands, while the last one was a new Schiff base reduced macrocyclic ligand. The three commercial ligands were ethylenediaminetetraacetic acid (EDTA), diisooctylphosphinic acid (DiOPA), and the anion-exchanger Aliquat 336 (methyltrioctylammonium chloride). The Schiff base reduced macrocyclic ligand was 3,6,9,12-tetraaza-4(1,2),11(1,2)-dibenzena-1(1,3)-pyridinacyclotridecaphane (TeDiPyDeca), which forms a very stable 1 + 1 copper complex Keq = 2 42 × 10 6 . This article presents the synthesis, Fourier transform infrared spectroscopy (FT-IR) studies, and crystal structure of the new copper complex Cu(TeDiPyDeca) as well as experimental data of solubility fitting with a Peng Robinson equation and van der Waals mixing rules. The molar volume of the solid (Vs), the vapor pressure (Pvap), and the binary interaction coefficient k ij of the four metal complexes were found. The physical effects of the molecular forms of the studied copper complexes were the most important factors in regard to solubility in SC CO 2 .